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High quantities of microplastic in Arctic deepsea sediments from the HAUSGARTEN observatory Melanie Bergmann, Vanessa Wirzberger, Thomas Krumpen, Claudia Lorenz, Sebastian Primpke, Mine B. Tekman, and Gunnar Gerdts Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b03331 • Publication Date (Web): 17 Aug 2017 Downloaded from http://pubs.acs.org on August 22, 2017

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Environmental Science & Technology is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

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Environmental Science & Technology

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High quantities of microplastic in Arctic deep-sea

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sediments from the HAUSGARTEN observatory

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Melanie Bergmann†,ǁ,*, Vanessa Wirzberger‡,§,ǁ, Thomas Krumpen⊥, Claudia Lorenz‡, Sebastian

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Primpke‡, Mine B. Tekman†, Gunnar Gerdts‡

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Zentrum für Polar- und Meeresforschung, Am Handelshafen 12, 27570 Bremerhaven, Germany

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*Corresponding author. E-Mail: [email protected]

HGF-MPG Group for Deep-Sea Ecology and Technology, Alfred-Wegener-Institut Helmholtz-

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Helmholtz-Zentrum für Polar- und Meeresforschung, Kurpromenade, 27498 Helgoland,

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Germany

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§

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Chemistry, Universitätsstrasse 5, 45141 Essen, Germany

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⊥Climate

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Meeresforschung, Bussestraße 24, 27570 Bremerhaven, Germany

17

ǁ

Department of Microbial Ecology, Biologische Anstalt Helgoland, Alfred-Wegener-Institut

University Duisburg-Essen, Faculty of Chemistry, Department of Instrumental Analytical

Sciences, Sea Ice Physics, Alfred-Wegener-Institut Helmholtz-Zentrum für Polar- und

Shared first authors

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ABSTRACT:

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Although mounting evidence suggests the ubiquity of microplastic in aquatic ecosystems

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worldwide, our knowledge of its distribution in remote environments such as Polar Regions and

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the deep sea is scarce. Here, we analyzed nine sediment samples taken at the HAUSGARTEN

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observatory in the Arctic at 2,340 – 5,570 m depth. Density separation by MicroPlastic Sediment

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Separator and treatment with Fenton’s reagent enabled analysis via Attenuated Total Reflection

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FTIR and µFTIR spectroscopy.

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Our analyses indicate the wide spread of high numbers of microplastics (42 – 6,595

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microplastics kg-1). The northernmost stations harbored the highest quantities, indicating sea ice

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as a transport vehicle. A positive correlation between microplastic abundance and chlorophyll a

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content suggests vertical export via incorporation in sinking (ice-) algal aggregates. Overall, 18

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different polymers were detected. Chlorinated polyethylene accounted for the largest proportion

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(38 %), followed by polyamide (22 %) and polypropylene (16 %). Almost 80 % of the

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microplastics were ≤ 25 µm.

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The microplastic quantities are amongst the highest recorded from benthic sediments, which

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corroborates the deep sea as a major sink for microplastics and the presence of accumulation

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areas in this remote part of the world, fed by plastics transported to the North via the

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Thermohaline Circulation.

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INTRODUCTION

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The contamination of our oceans with plastic debris is a problem of growing

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environmental concern. Recently, it was estimated that 8,300 million metric tons (MT) of plastics

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have been produced to date, 6,300 MT of which have become waste as of 2015.1 Between 4.8

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and 12.7 million MT of plastic debris entered the ocean from land in 2010.2 However, 99 % of

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this debris have not been captured by global litter estimates.3 It has been speculated that a large

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fraction of plastic debris may escape our sampling gears because of uptake and transport by

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biota, accumulation on the largely inaccessible deep seafloor and in other remote environments

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or by fragmentation into smaller particle sizes. In the marine realm, the integrity of plastics is

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compromised through mechanic abrasion, interaction with biota, UV radiation and temperature

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fluctuations such that it brittles and fragments.4 Particles smaller than 5 mm are considered

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microplastics (MPs).5 Sources for plastic in the oceans can be anthropogenic waste, which is

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dumped directly into the sea by fishers and other ships, aqua culture, ship yards, beach visitors,

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daily care products and washed out fibres from synthetic textiles. Municipal drainage systems,

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road runoff and rivers represent additional entry points.6

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Although MPs were discovered as early as in the 1970’s

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the scientific research

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intensified only after time-series data highlighted increasing MP contamination of Atlantic waters

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and MP ingestion by marine biota.8 Since then, MP has been identified in all marine realms from

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beaches to the deep seafloor and in all oceans and seas worldwide.9, 10 Plastic in this size range

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is of particular concern because it can be taken up by a wider range of biota (>172 species) and

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be propagated in food webs.9 While some organisms excrete MP without any apparent effect,11

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in others ingested MP may interfere with food uptake and transfer adsorbed and added toxins.9

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In addition, MP between 0.5 and 438 µm may translocate to organs or blood

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effects. Despite increased research efforts, however, the overall ecological consequences of

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MPs are still not clear.

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12-14

amongst other

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The discovery of oceanic gyre-associated accumulation zones, so called ‘garbage

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patches’,15 also stimulated intensified research efforts. Five such systems were confirmed to

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date and the suspected presence of further accumulation zones in the Arctic

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corroborated.17 Cózar et al. reported increasing plastic concentrations towards the northernmost

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borders of the Greenland Sea due to the barrier imposed by the ice sheet.17 One of these zones

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west of Svalbard happens to be close to the HAUSGARTEN observatory, from which increasing

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litter quantities were recorded on the deep seafloor between 2002 and 2014.18, 19 Litter and MP

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were also recorded from the nearby sea surface.20,

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quantities of MPs (Peeken, unpubl. data).22 Tekman et al. reported increasing numbers of

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smaller-sized plastic items (< 10 cm) on the deep seafloor.19 Although the deep seafloor may

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constitute a major sink for MP until now only three studies were dedicated to MP in deep-sea

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sediments at depths between 1,000 – 5,800 m from the Nile Deep Sea Fan, Southern Ocean,

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Porcupine Abyssal Plain, Mediterranean Sea, SW Indian Ocean, NE Atlantic Ocean and the NW

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Pacific Kuril-Kamchatka Trench.23-25

21

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was recently

In addition, Arctic sea ice contains vast

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The aim of this study is to quantify MP pollution on the Arctic seafloor in the

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HAUSGARTEN observatory along a bathymetric transect ranging from 2,500 - 5,500 m depth.

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Sediments taken along a latitudinal gradient were also analyzed to assess the importance of MP

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release due to melting processes in the marginal ice zone. To attempt source allocation, the

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polymer composition of all particles identified is described and compared. In the absence of a

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standard operation procedure for the analysis of MP from sediments,5 a new method was

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adopted to remove organic material (Fenton’s reagent) prior to analysis by Fourier-transform

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infrared (FTIR) spectroscopy.26

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MATERIALS AND METHODS

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Study area. The sediments analyzed during this study were taken from the Long-Term

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Ecological Research (LTER) observatory HAUSGARTEN in the summer of 2015 during

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expedition ARK 29.2 of the research icebreaker RV Polarstern. HAUSGARTEN was established

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by the Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research in 1999 in the

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Fram Strait at N79°, west of Svalbard (Norway). It currently comprises 21 sampling stations

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along a latitudinal and a bathymetric gradient between 250 – 5,500 m water depth.27 These

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stations are subject to annual sampling campaigns targeting all ecosystem compartments from

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the sea surface to the deep seafloor. The Fram Strait represents the only deep-water connection

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between the North Atlantic and the Arctic Ocean. The HAUSGARTEN area is affected by warm

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Atlantic waters transported by the West Spitsbergen Current in the upper 500 m, which is fed by

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the north Atlantic waters, such that the area is ice-free for most of the year. Still, the northern

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HAUSGARTEN stations N3 and N5 are covered by ice during winter, but ice can also be present

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during summer when it is carried from the Central Arctic into the Fram Strait by the Transpolar

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Drift.19 Below the warm Atlantic water layer, there are low-temperature waters modified by polar

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water masses.28

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Sediment sampling. To obtain virtually undisturbed sediment samples, a video-guided

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multiple corer (MUC; Oktopus GmbH) holding eight cores of 100 mm diameter was used. Three

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stations were sampled along the latitudinal gradient (N5, N3, S3), which runs along the 2,500 m

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isobath (Table 1, Figure 1). These include the northernmost station N5, which is located in the

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marginal ice zone. Six samples were taken at stations from the bathymetric gradient (HG-IV –

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IX: 2,342 – 5,570 m water depth), including the Molloy Deep, the deepest part of the Arctic

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Ocean (Table 1, Figure 1). Depending on availability, the top 5 cm of 3 – 6 sediment cores were

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sliced off with a metal spatula and frozen in tin foil. Three additional samples were taken from

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different MUC cores with cut-off syringes and analyzed at 1-cm intervals down to 5 cm sediment

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depth. The bulk pigments registered by this method are termed chloroplastic pigment 5 ACS Paragon Plus Environment

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equivalents and indicate phytodetrital input to the seafloor.29 They were extracted in 90%

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acetone and measured with a Turner fluorometer.30, 31

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In the laboratory, frozen sediments from all the cores of each station were defrosted,

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pooled and homogenized. Before the separation, the dry weight was determined by weighing

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three

sub-samples

from

each

sample

before

and

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after

drying

at

60 °C.

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Table 1. Details of sediment sampling at HAUSGARTEN stations, biogeochemical parameters and prevailing summer sea ice conditions. S3

HG-IV

HG-V

HG-VI

HG-VII

HG-VIII

HG-IX

N3

N5

PS93/48-11

PS93/50-19

PS93/51-4

PS93/53-3

PS93/54-2

PS93/55-2

PS93/56-1

PS93/85-2

PS93/60-10

Date (dd/mm/yy)

25/07/15

27/07/15

28/07/15

28/07/15

29/07/15

29/07/15

29/07/15

11/08/15

03/08/15

Latitude (N)

78°35,98'

79°04,91'

79°03,81'

79°03,61'

79°03,63'

79°3,86'

79°08,02'

79°36,25'

79°56,28'

Longitude (E)

5°04,07'

4°08,59'

3°39,46'

3°34,98'

3°28,56'

3°20,10'

2°50,58'

5°10,28'

3°11,60'

2,342

2,460

3,127

3,430

4,092

5,108

5,570

2,783

2,549

0.00

0.79

0.79

0.79

0.79

2.61

2.61

3.47

35.33

0

2

2

2

2

8

8

13

84

60.54

53.86

51.01

47.26

42.34

36.91

60.72

58.97

60.48

1.25

1.38

1.42

1.30

1.38

1.45

1.11

n.a.

1.33

13.19

15.40

14.73

13.86

14.03

17.53

18.35

n.a.

17.71

0.78

0.66

0.74

0.61

0.59

0.68

1.09

0.88

0.88

4.75

20.53

51.81

16.01

9.63

6.67

10.22

33.76

8.53

Sampling cast

Depth (m) Mean ice concentration (%) Duration of ice coverage (days) Porosity (%) Chlorophyll a (µg cm-3) Chloroplastic pigment equivalent (µg cm-3) Particulate organic carbon (%) -1

Phospholipids (nmol ml )

7

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Sediment characterization and separation. The MicroPlastic Sediment Separator

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(MPSS; HYDRO-BIOS GmbH) was used to separate the denser sediment particles from the

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less dense MP particles.32 A ZnCl2 solution (1.7 – 1.8 g cm-3 density) was filtered into the

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MPSS using cartridge filters (10-µm stainless steel and 1-µm pleated PP; Wolftechnik

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Filtersysteme GmbH & Co. KG) each time prior to the addition of sediments. A steel rotor on

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the bottom of the MPSS mixed the sediment at ~12 rpm for 35 – 60 min. The MPSS was

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filled to the lower half of the dividing chamber after the rotor had been turned off to avoid

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overflow of the sample. After 12 h, the MPSS was filled up to the upper part of the dividing

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chamber and left for 7 h. Finally, the ball valve between the two dividing chambers was

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closed and the ZnCl2 solution above the ball valve was rinsed with Milli-Q into a glass bottle

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with glass cap and stored at 4 °C until further analysis.

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Preparation of the samples prior to analysis. A filtration step was required to

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remove the ZnCl2 solution and to separate the sample into particle size fractions larger and

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smaller than 500 µm since µFTIR analysis in transmission mode can only identify particles
500 µm). The large size fraction was sorted using a

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stereomicroscope (Olympus SZX16) and Bogorov chamber (10.5 × 7.3 cm) before analysis

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by attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) of suspect

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MP particles. Each sample was assessed at 16-fold and some particles even at 32-fold

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magnification. Generally, particles of clear and homogeneous colouration and without cellular

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or organic structure were selected for analysis by ATR-FTIR.33 The size of all particles was

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determined by measuring the longest dimension with the cellSens software (Olympus).

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Currently, fibers cannot be well discerned by the applied Fourier-transform infrared 8 ACS Paragon Plus Environment

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microscopy (µFTIR) analytical method, which was used for the small size fraction (s. below).

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Therefore, they were also omitted in the analysis of particles of the large size fraction.

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Small size fraction (< 500 µm). While previous studies relied on enzymatic

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digestion, H2O2, acid or alkaline treatments to reduce organic material prior to spectroscopic

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analysis 34-36 Fenton’s reagent (FeSO4 in combination with H2O2) was recently suggested as a

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promising alternative agent.26 The small size fraction was thus treated with Fenton’s reagent

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to remove organic matter prior to µFTIR analysis. Briefly, a 7.2 mM FeSO4 solution (pH 500 µm) using a Tensor 27

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spectrometer (Bruker Optics GmbH) including a platinum ATR unit (wave number range:

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400 – 4,000 cm-1, 4 cm-1 resolution, 6 mm aperture, 32 scans). After measurement, the

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spectrum was compared against reference spectra through a library search with the software

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Opus 7.5. Particles with a hit quality above 700 (max. of 1,000 hit quality) were accepted as

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verified polymers. The library is available upon request.

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The small size fraction (< 500 µm) was measured by a TENSOR 27 spectrometer

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(Bruker Optics GmbH) connected to a Hyperion 3000 µFTIR microscope equipped with a

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focal plane array (FPA) detector with 64 × 64 detector elements. An infrared range of 1,250 –

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3,600 cm-1 was used for measurements. Six scans were performed per field at a resolution of

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8 cm-1 and a binning factor of 4 (see 37 for setting details). 9 ACS Paragon Plus Environment

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After drying for at least two days (30 °C) the filter was placed under the FTIR-microscope

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onto a calcium fluoride window and an overview image was recorded. Subsequently, the

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concentrated filter area (166 mm², 73 × 73 FPA fields, 1.36 million spectra) was measured,

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which took ca. 13 h.

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Automated analysis of µFTIR data. The data were processed by automated

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analyses of µFTIR data.38 Briefly, each spectrum in the measurement file was analyzed via

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two library searches to confirm polymer identity. The library is available upon request. Each

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pixel identified was stored with its position, analysis quality and polymer type into a file, which

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was subject to image analysis based on Python 3.4 scripts and Simple ITK functions.38 This

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combination enabled the identification, quantification and size determination of all polymer

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particles in a sample and additionally excluded human bias.38 To reduce the complexity of

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the size distribution the analysis introduced size classes (for details see 38).

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Contamination protection. If not stated otherwise all laboratory ware used was

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made of glass or stainless steel and thoroughly rinsed with Milli-Q before use. All polymer-

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based items, which could not be replaced by alternative glass items (e.g. bottle caps, filter

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holders) were made of polytetrafluoroethylene (PTFE). Dustboxes ® (DB1000, G4 pre-

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filtration, HEPA-H14 final filtration, Q = 950 m³/h, Möcklinghoff Lufttechnik), which filter

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airborne particles, were installed in laboratories for density separation, particle sorting and

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FTIR analyses. All filtration steps were performed in a laminar flow cabinet (Scanlaf Fortuna,

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Labogene), except for the ZnCl2 filtration by cartridge filter, to prevent airborne

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contamination. All chemicals (e.g. FeSO4, H2O2) were filtered through polycarbonate filters

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(0.2 µm pore size, Merck Millipore, IsoporeTM GTTP) to remove particulate contaminants

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before usage. To remove contaminants from the MPSS it was filled with ZnCl2 and left to

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settle for 5 h. The upper layer of the ZnCl2 solution (above the ball valve) was discarded prior

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to the addition of the next sample. Cotton laboratory coats were generally worn to reduce

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contamination from synthetic textiles. Latex gloves were worn for safety at work. To account

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for possible process contaminations in the evaluation of the samples, a procedural blank was

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run. For this purpose, an empty glass jar was rinsed with ZnCl2 into the MPSS instead of 10 ACS Paragon Plus Environment

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adding sediment and all the following procedures (filtration, purification and analysis) were

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performed in the same way as for the other samples. The amounts of MPs determined in the

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samples were blank-corrected by calculating the amount of MPs in 100 % of the sample

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volume (volume of samples analyzed by µFITR: S3 = 1.99 %; HG-IV = 3.62 %; HG-V = 1.84

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%; HG-VI = 2.29 %; HG-VII = 3.96 %; HG-VIII = 4.21 %; HG-IX = 67.7 %; N3 = 1.25 %; N5 =

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1.85 %) and subtracting the amount of MPs determined in 100 % of the blank. The number of

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particles kg-1 was calculated for each sample based on the amount of dry sediment.

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Sea-ice concentration. To test for a correlation between the presence of sea ice

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above the sample location and MP deposition, sea-ice concentration data were obtained by

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the Centre for Satellite Exploitation and Research (CERSAT) at the Institut Français de

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Recherche pour l’Exploitation de la Mer (IFREMER), France.39 The ice concentration was

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calculated based on the ARTIST Sea Ice (ASI) algorithm developed at the University of

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Bremen, Germany.40 Sea-ice concentration data from all HAUSGARTEN stations (Table 1)

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were extracted for the summer months (May – July 2015) over an area of 12.5 × 12.5 km.

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From this, the mean summer ice concentration and the days of sea ice coverage were

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calculated for each station.

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Data analysis. The MP counts of the large and small size fractions were combined

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for data analyses. Since different sediment quantities were sampled from different stations

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the data were converted to MP kg-1. In the current absence of established standards, MP

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counts were additionally converted to MP L-1 and MP cm-2 to enable comparison with

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published data given per unit volume and area although the latter may introduce variability

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because of differences in the sample volumes used. The polymer composition and MP

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particle size distribution of the different samples was compared by hierarchical cluster

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analysis (PRIMER-e version 6.1.6) based on group average linkage of Bray-Curtis similarity

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of square-root transformed polymer abundance data.41 Polymer diversity was computed

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based on Shannon Wiener diversity (log base e). We tested for Pearson’s correlations

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between chlorophyll a content (mean of the 5-cm sections) and MP quantity as well as

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polymer diversity after establishing a normal distribution of the data using Anderson-Darling 11 ACS Paragon Plus Environment

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tests (Minitab 14; p > 0.05). Mean summer ice concentrations and number of days of sea ice

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coverage were used for Spearman's rank correlation tests with MP quantities and diversity

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for each station (Minitab 14).

232 233

RESULTS

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Microplastic quantities. MPs were detected in all sediment samples with an overall

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mean number of 4,356 (± 675 standard error) particles kg-1 sediment. The highest numbers

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were found at the two northern stations N3 (6,595 MPs kg-1) and N5 (6,348 MPs kg-1),

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followed by HG-V (5,568 MPs kg-1), HG-VIII (5,390 MPs kg-1), the southernmost station S3

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(4,520 MPs kg-1), HG-IV (4,050 MPs kg-1), HG-VII (3,856 MPs kg-1), HG-VI (2,834 MPs kg-1)

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and lastly by the deepest station HG-IX (42 MPs kg-1) (Figure 1; Table 2). It should be noted

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that the MP counts from HG-IV and N3 may be slightly underestimated due to slight sample

241

loss during preparation. All results presented are blank corrected.

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Figure 1. Abundance and composition of microplastics detected in sediments from the Artic

244

deep sea (log scale, see Table 2 for abundance data).

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Polymer composition. Eighteen different polymer types were identified in total from

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all sediment samples (Table 2). In the larger size fraction (> 500 µm), 177 potential plastic

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particles were analyzed, of which 31 were identified as plastic polymers (17.5 %). The 13 ACS Paragon Plus Environment

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remaining particles could not be identified as they had a hit quality below 700 except for one

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cellulose particle and a particle identified as wild boar. While all plastics in this size fraction

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were identified as polytetrafluoroethylene (PTFE), there was great variability in the polymer

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composition in the small size fraction (< 500 µm) with 18 different types found in total ranging

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between 5 (HG-IX) and 14 (HG-VIII) types per sample (Table 2). Since PTFE cannot be

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detected within the spectral region of 3600 – 1250 cm-1 available for the particles < 500 µm in

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µFTIR, no statement on the presence or absence of PTFE in the small size fraction can be

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made. The polymer composition of the deepest station HG-IX, which was dominated by

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polypropylene (Figure 2) and nitrile rubber shared only 11 % similarity with the other stations

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(Figure S1). The southernmost station, S3, harbored a polymer composition, which was 63 %

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similar to the remaining samples (Figure S1) and characterized by a great proportion (62 %)

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of chlorinated polyethylene. The remaining samples had a 70 – 80 % similar polymer

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composition (Figure S1). Polypropylene, nitrile rubber and PTFE occurred in all samples but

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polyamide and chlorinated polyethylene were also detected in eight out of nine samples. In

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terms of overall particle numbers from all stations, chlorinated polyethylene accounted for the

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largest proportion (38 %), followed by polyamide (22 %), polypropylene (16 %) and nitrile

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rubber (8 %) (Table 2). This is also reflected in the polymer composition from different

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stations as summarized in Figure 1.

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Table 2. Microplastic abundance (number), diversity (Shannon-Winer H) and composition in sediments from different HAUSGARTEN stations. To

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enable comparisons total MP kg-1 was converted to MP per area and volume. Polymer abundance in the samples refers to number kg-1 dry

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sediment of the sample; polymer abundance in the blank refers to 100 % sample volume of the blank. All values are procedural blank corrected.*

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slight sample loss. S3

Total MP abundance kg-1 MP abundance (>500 µm) kg-1 Total MP abundance cm-2 Total MP abundance L-1 Polymer diversity (H) Polyethylene chlorinated

HG-IV*

HG-V

HG-VI

HG-VII

HG-VIII

4520.22 4049.87 5568.02 2834.03 3855.99 5390.67

HG-IX

N3*

N5

41.76

6594.56

6348.27

Blank

Blank

(>500 µm)

( 5 mm (~22 %).42 Sediments collected at 15 locations along the densely populated

327

areas off the Belgium shelf (100 – 3,600 MPs kg−1)

328

3,146 MPs kg-1)

329

Lagoon in Italy (2,175 MPs kg-1) 45 and the Belgian coast (390 MPs kg-1).46 19

44

43

and the Dutch North Sea coast (54 -

approached more similar MP quantities as did sediments from the Venice

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Still, overall the abundance of MP in the deep Fram Strait appears to be higher than

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in all other benthic regions investigated. Some of the observed differences may be due to

332

differences in the methodology used. Unlike coring devices, for example, grabs produce a

333

bow wave when lowered to the seafloor, which flushes the top sediment layer aside

334

preventing the detection of recently deposited pollutants. In addition, the MPSS recovers

335

significantly more MP compared with other separation methods, especially in the small size

336

range.37 All of the above studies relied on the analysis of visually pre-selected particles. Our

337

data showed, however, that nearly 80 % of the MPs were smaller than 25 µm. This

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significant proportion would have gone unnoticed leading to serious underestimates. Despite

339

these methodological differences the high abundance of microplastics in the deep-sea

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sediments of the remote Arctic Ocean is striking.

48

341

Still, even if a more sensitive methodological approach allowed us to detect higher

342

MP quantities the magnitude of the differences indicates that HAUSGARTEN may be in or

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close to a plastic accumulation area. Similar MP numbers were recorded near the sea

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surface southwest of Svalbard using an underway sampling device and visual pre-selection

345

(21 converted: 2,680 MP L-1). Recently, high numbers of small plastic debris were also

346

reported from the sea surface in the Fram Strait pointing to an accumulation area south of

347

HAUSGARTEN.17 It was suggested that a significant fraction of this debris likely originated

348

from Northern Europe and was transported to the North with the Thermohaline Circulation.

349

Still, inputs from local sources may increasingly also contribute to this since anthropogenic

350

activities such as fisheries and tourism have increased markedly due to the receding sea

351

ice.19 Plastic debris from fisheries nowadays dominates on the beaches of Svalbard.47 The

352

release of MP entrained in Arctic sea ice during melting processes

353

considered another reason for the high MP quantities recorded although this has to be

354

verified, for example, by analysis of samples from year round moored particle traps.48

355

Differences

between

HAUSGARTEN

stations.

22

The

in the region can be

two

northernmost

356

HAUSGARTEN stations N3 and N5 contained the highest MP numbers. Both stations are

357

located within or close to the marginal ice zone, as shown by the highest ice concentration 20 ACS Paragon Plus Environment

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358

and duration of sea ice coverage. Arctic sea ice entrains enormous quantities of MP 22 during

359

ice formation in the Central Arctic and may act as transport vehicle: after the ice breaks up in

360

the Central Arctic in spring it is transported to the south as ice floes with the Transpolar Drift.

361

On route, it encounters warmer Atlantic surface waters and continues to melt possibly

362

releasing entrained MPs. Depending on the sinking velocity, there may be some horizontal

363

displacement of particles from their point of origin at the sea surface as they descend to the

364

seafloor. However,

365

catchment areas. Increasing numbers of small plastic fragments (< 10 cm) were also

366

recorded on seafloor photographs at N3.19 The number of MP at the two northern stations

367

may thus be higher because they receive MP from meltwater as well as distant sources

368

through the Thermohaline Circulation.

49

reported fast sinking rates for some MP implying reasonably small

369

The other HAUSGARTEN stations may harbor a lower MP load because they receive

370

MPs primarily only through the Thermohaline Circulation, whereas the northern stations are

371

affected by both Atlantic waters and meltwater carrying MPs. The positive correlation

372

between MP levels and chlorophyll a content suggests that Algae play a role in the

373

downward transport. It should be noted that there was no significant correlation with total

374

phytodetrital input, which also includes phaeophytin, an indicator of refractory material. This

375

highlights the potential role of freshly deposited algal rather than older material. Indeed, the

376

vertical transport of originally positively buoyant MPs may be accelerated significantly by the

377

presence of aggregating Algae.50, 51 In the study area, the ice algal diatom Melosira arctica

378

forms dense aggregates beneath the sea ice. During melting, such aggregates may entrain

379

MP and rush to the deep seafloor

380

waters carry increasing amounts of the colony forming algae Phaeocystis pouchetii to

381

HAUSGARTEN 27, 48 whose polysaccharide gel matrix may entrain buoyant MP, too.

52

facilitating the deposition of MPs. In addition, Atlantic

382

The low quantities of MP in the Molloy Deep, the deepest depression of the Arctic,

383

were surprising. If nothing else, higher MP levels were expected because of the funnel-

384

shaped surrounding topography and the presence of downwards directed eddy systems, all

385

favouring the accumulation of MPs. It could be argued that MP export is attenuated with 21 ACS Paragon Plus Environment

Environmental Science & Technology

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386

depth as is the vertical export of particulate organic matter.53 However, the third highest MP

387

concentration recorded at the nearby station HG-VIII at similar depth (5,100 m, 12 km

388

distance) contradicts this notion. Another possibility is that MPs have evaded our detection

389

because they were already incorporated in an exceptionally high standing stock of infaunal

390

meiofauna

391

primarily of the deposit-feeding sea cucumber Elpidia heckeri.55 Recently, epibenthic

392

megafauna including sea cucumbers from the deep SW Indian Ocean and equatorial mid-

393

Atlantic were shown to ingest MP.56 Microplastic abundance in North Sea and English

394

Channel sediments was influenced by other factors including carbon content and grain size.44

395

By contrast, at HAUSGARTEN, neither organic carbon content nor porosity appeared to be

396

correlated with MP numbers. Of the parameters tested, only chlorophyll a and marginally

397

possibly also summer sea-ice concentration appeared to be correlated although low sample

398

sizes may have obscured possible correlations. As stated above, this could be seen as an

399

indication of enhanced vertical transport via incorporation in fast-sinking ice-algal

400

aggregates. Still, samples from the water column or experimental work are required to

401

establish mechanistic links. In addition, further benthic studies are needed to assess if the

402

wider Arctic region is contaminated with MP or if the Fram Strait area is an accumulation

403

zone.

54

and epibenthic megafauna, which distinguishes this station and consists

404

Particle composition. Polypropylene, nitrile rubber and PTFE occurred in all

405

samples but polyamide and chlorinated polyethylene were also detected in eight out of nine

406

samples. In terms of overall particle numbers from all stations, chlorinated polyethylene

407

accounted for the largest proportion (38 %), followed by polyamide (22 %), polypropylene

408

(16 %) and nitrile rubber (8 %). Since the density of PTFE (2.10 – 2.30 g cm-3),

409

rubber (1.3 g cm-3) and polyamide (1.13 g cm-3) exceeds the density of sea water (1.02 – 1.03

410

g cm-3)

411

chlorinated polyethylene have a lower density

412

including eddies and wind mixing,58 biofouling, incorporation in sinking aggregates and

413

vertical transport with biota or faeces must counteract their buoyancy. Polypropylene and

4

57

nitrile

these MPs are likely to sink to the seafloor directly. By contrast, polypropylene and 4

such that a combination of processes

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Environmental Science & Technology

59

414

polyethylene are the most widely demanded plastic types in Europe

415

e.g. packaging and fishing gear.4 Therefore, its prevalence does not come as a surprise.

416

These two polymer types accounted also for almost half of the MPs from Atlantic surface

417

waters.57 Microplastics from surface waters southwest of Svalbard contained polyester (15

418

%), polyamide (15 %), acrylic (10 %), polyethylene (5 %) and polyvinyl chloride (5 %).21

419

Polyethylene and to a lesser degree also polyamide dominated MP in Arctic sea ice sampled

420

in 2014, one year before our sediment sampling, especially in the two cores from the Fram

421

Strait (Peeken, unpubl. data). All polymers detected in the ice cores or surfaces waters of the

422

Arctic Ocean (except acrylic) have been also detected in the deep-sea sediments of the

423

Arctic Ocean. This indicates that both surface waters and sea ice are possible sources of MP

424

found in the sediment at HAUSGARTEN. Only few previous studies analyzed the

425

composition of the polymers identified. Polyester followed by acrylic fibers dominated in

426

sediments from the deep NE Atlantic, Mediterranean, SW Indian Ocean samples and

427

subarctic sites.25 Central Arctic ice cores were also characterized by a different MP

428

composition, which was dominated by polyester (21 %) and nylon/polyamide (16 %),

429

polypropylene (3 %), and then by 2 % each of polystyrene, acrylic, and polyethylene.22 Still,

430

the majority of particles were fibers, which were not considered in the present study. Other

431

studies on MP in the deep sea did not describe the polymer composition.23, 24 Unfortunately,

432

the abundance of coal particles could not be determined but such particles were also

433

reported before in deep-sea sediments between New Zealand and Antarctica (5,314 m

434

depth) and the Porcupine Abyssal Plain (4,100 m depth)

435

Subarctic Ocean.61 The latter was attributed to atmospheric deposition and fluvial discharge,

436

as ice-rafted material, coastal erosion, and the adsorption of dissolved black carbon onto

437

particles.

60

and widely used for

as well as from the Arctic and

438

Polymer Size. Overall, 83 % of the analyzed particles in the large size fraction (> 500

439

µm) were not identified as polymers. This highlights once more a likely overestimation of MP

440

particles when relying exclusively on visual identification.37 At the same time, it cannot be

23 ACS Paragon Plus Environment

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Page 24 of 34

441

excluded that some particles may be overlooked during the visual identification step leading

442

to an underestimation.

443

The analysis of the particles in the large size fraction showed also differences

444

compared to others studies reporting particles > 500 µm. While other studies detected

445

particles with striking colors as well as white, black, grey and translucent particles

446

PTFE particles were identified in this study that were white, black or grey. By contrast,

447

particles of a striking color were not identified as polymers showing once again the need for

448

spectroscopic methods for a reliable identification of polymers.

62, 63

only

449

As stated above, some 80 % of the MPs were ≤ 25 µm. The size structure of MP

450

particles was steadily increasing in numbers towards lower sizes with no sign of saturation

451

towards the lower size end. This may indicate that deep-sea sediments contain even more

452

particles in yet smaller particle sizes, which have evaded our detection and that of previous

453

studies. In Atlantic surface waters, the majority of MP particles (64 %) detected were
100 µm) are translocated to organs of the tropical fiddler crab

574

Uca rapax. Mar. Pollut. Bull. 2015, 96, 491-495.

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(14) Farrell, P.; Nelson, K., Trophic level transfer of microplastic: Mytilus edulis (L.) to Carcinus maenas (L.). Environ. Pollut. 2013, 177, 1-3.

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(15) Moore, C. J.; Moore, S. L.; Leecaster, M. K.; Weisberg, S. B., A comparison of plastic

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and plankton in the North Pacific Central Gyre. Mar. Pollut. Bull. 2001, 42, (12), 1297-1300. 28 ACS Paragon Plus Environment

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